Paraffin alkylation process



Patented Apr. 27, 1 943 UNITED STATES PATENT/OFFICE PABAFFIN ALKYLATION PROCESS Clarence J. Ott, San Francisco, Calif assignor to Shell Development Company, San Fran Calif., a corporation of Delaware cisco,

' No Drawing. Application September 27, 1941,

Serial No. 412,681

a Claims. (c1. 196-10) The alkylaticn oi isoparaillns such as isobutane, isopentane and the like by reaction with oleflnes, particularly normally gaseous oleflnes, is carried out on a large scale. Concentrated sulfuric acid is the most generally used catalyst butother alkylation catalysts such as aluminum chloride, hydrogen fluoride, boron trifluoride, halosulionic acids such as chloro. and fluorosulphonic acids, hydrofluoroboric acid, etc., have alsobeen used. It is an obiectof the present invention to provide an improved method for carrying out such reactions by means of new -alkylating agents which offer advantages over the previously used oleflnes.

According to the invention the alkylation of open and closed chain parafllns is eifected by reacting such paraillns, in-the presence of an alkylation catalyst, with esters of organic acids having dissociation constants greater than 2X10 and most preferably greater than 5x10 By this method of operation, the dimcultles and undesirable features involved in the use of oleflnes as alkylating agents are avoided. 1

While the exact mechanism of the reaction involved has not been fully determined, the results obtained with esters of alcoholshaving at least two carbon atoms per molecule can be explained by assuming that in the presence of an alkylatable saturated hydrocarbon and an alkylation catalyst such esters of strong organic acids such as formic, oxalic, trichloracetic and the like undergo scission with formation of free organic. acid and an oleflne. The latter immediately reacts with the saturated hydrocarbon so that the concentration of oleflne in the reaction mixture is kept very low at all times and there is much less tendency for the catalyst to be deactivated'by side reactions than is the case when oleflnes are used as alkylatlng agents. Whatever may be the true explanation of the changes taking place, the use of esters of organic acids hav. ing dissociation constants greater than 2 10-. is capable of giving greatly improved results not only with respect to the life of the alkylation catalyst used but also in regard to the yield and quality of product obtained.

The process of the invention may be applied to the alkyiation of open or closed chain all It deals with an improved,

phatie hydrocarbons, particularly those containing a hydrogen atom attached toa tertiary'carbon atom and suitable substitution products thereof, although by the use of alkylation cata lysts which are capable of isomerizing normal parafllns under the reaction conditions, for example aluminum chloride, such parafllns may be alleviated by the new procedure. Thus, it may be used for the manufacture of other branched chain compounds from isobutane, isopentane, 2- methyl pentane, 2,3-dimethyl butane, 2,2,5-trimethyl hexane, 3-ethy1' pentane, methyl cyclopentane, methylv cyclohexane, 1,4-dimethyl cyclohexane, I-ehIoro-S-methylbutane and the like, or from the corresponding unbranched compounds.

two or more such compounds or mixtures containing such a compound with other components which may or may not'be inert under thereaction conditions but which do not inhibit the desired alkylation. Particularly advantageous sources of starting material for the process of the invention are hydrocarbons whichma'y be derived from petroleum, petroleum products, shale oil, coal' or other carboniferous-materials. The

straight and/or branched chainalkylatable satu'- rated compounds present in the starting material may be of natural occurrence, the result or pyrogenetic treatment, hydrogenation, isomerization or other suitable processing. Cracked petroleum distillates or special fractions thereof,

particularly hydrocarbon fractions consisting of or predominating in hydrocarbons containing the samenumber of carbon atoms per molecule may be used although non-isomeric mixtures such as gasoline fractions are also suitable. Such fractions or mixtures may advantageously be subjected to. suitable refining. for the removal of;

sulfur and/or nitrogen or oxygen compounds or other undesirable impurities prior to use in the process of the invention. Removal of the more reactive hydrocarbons such as aromatic and/orunsaturated hydrocarbons may also be desirable. Thus, the extraction process of United States.

Patent 2,114,524, for example, may be used to decrease the aromatic content of the material to be alkylated and/or'oleflnes may be removed by extraction as described in Patents 1,893,733," 2,007,159 and 2,060,143 or-by polymerization as shown in Patents Whether or not one or' more sucl'i pretreatments of the feed stock is applied, it may be advantageous to further increase the concentration of the saturated aliphatic compound betherefrom.

groups."

ing reacted by fractionation and/or isomerization of isomeric hydrocarbons present therewith.

For the purpose of making the invention more clear it will be described in detail in connection with the use of concentrated sulfuric acid, preferably acid of 90%-100% concentration, as the alkylation catalyst since its low first cost and ready availability make this a particularly advantageous catalyst. It will be understood, however, that the invention is not limited thereto as similar, or in some cases even relativelygreater, advantages may be obtained when the process is applied to alkylations carried out with other acid alkylation catalysts such as hydrogen fluoride, chlorosulfonic, fluorosulfonic, bromosulfonic, and hydrofluoroboric acids. Furthermore, not only may mixtures of such catalyst acids be used, but also mixtures of one ormore acid alkylation catalysts with other materials having a beneficial effect on the reaction, such for example as boron fluoride, copper and/or magnesium sulfates, the oxides of elements, of group V of the periodic table, e.'g. phosphorus pentoxide, an oxide of vanadium, etc., zinc or cadmium phosphates, sulfur dioxide and/r trioxide, or othersuitable compounds. Instead of acid catalysts alkylation catalysts of the Friedel- Crafts type such as aluminum halides or organic or inorganic complexes thereof, zinc chloride and i the like may also be used.

most preferably esters of aliphatic carboxylicacids are used, althoughesters having substituted aromatic' groups which sufllciently inhibit side fled and the product recovered without dilution of the reaction mixtur as therein described, it is feasible to use the entire upper layer of the esterification mixture as feed to the alkylation system. In this way any unesterified olefines may be recovered and used for alkylation along with the esters. Any undesirable constituents, for example diluent parafiins, present may be removed from the upper layer of the esterification mixture before it is used in the alkylation step of the process. Where different catalysts are used for the esterification and alkylation steps it may be advantageous to separate the esterification catalyst acid from the esters, as by the procedure claimed in United States Patent 2.04:2,218,

. prior to their use as alkylation agents. The acid reactionsof the aromatic group may be employed. Most preferably esters of carboxylic acids at least as strong as formic acid are employed. Suitable esters are, for example, the methyl, ethyl, normaland.,isopropyl, normal, secondary, tertiary and isobutyLthe amyl, hexyl and higher esters of formic, malic, citric, tartaric, malonic; oxalic, trimethyl sulfanilic, the haloacetic and halo-propionic acids, and the'like. These preferred types of esters are cited by way of illustration only and it is to be understood that other esters of analogous strong organic acids, for example substitution products of the foregoing esters such as the corresponding halogenated esters or the like may also be used and'substituted alkylation-products, such for example as. halogenated alkylation products, obtained hereinafter generically will be understood as including the introduction into paramn molecules of either substituted or unsubstituted alkyl While the invention is not restricted with respect to the origin of the esters of strong organic acids used for alkyiating' the chosen paraffin, a particularly advantageous source of suitable esters is reactiq: of oleflnes with strong carboxylic acids in the presence of asuitable alkylation acid catalyst such as sulfuric or hydro-- 'fluoric acid or the like.

An especially useful method of carrying out such reactions is described, for example, in United States Patent 2,006,734. Whether or not the oleflnes are; esteri- The expression "alkylating as usedv chloride and th like.

catalyst used for the esterification may be advantageously acid which has been employed in the alkylation step of the process.

The temperature at which the reaction of the chosen ester and parafiin is most advantageously carried out will depend upon the nature of these reactants as well as upon the type of catalyst adopted and its concentration. With sulfuric acid of about to concentration, temperatures of the order of about 0 C. to 49 C. may be used, the lower temperatures being preferably employed with the more concentrated acid and the temperature being increasedas the acid concentration is reduced. Similar temperatures may be employed in the presence of aluminum With halosulfonic acid catalysts lower temperatures are generally preferable. Using a mixture of equal molecular amounts of boron fluoride and water as the catalyst, it is feasible to employ somewhat higher temperatures and even higher temperatures are desirable when employing less active catalysts.

The process may be carried out with both reactants in thevapor phase but more preferably at least the paraffin to be alkylated is maintained in the liquid phase. The preferred procedure is to maintain all reactants in the liquid state throughout the reaction. It is desirable to have a relatively. large amount of liquid catalyst acid present, for example about. 0.5 to 2 volumes, or preferably 0.7 to 1.3 volumes, of catalyst acid per volume of reaction mixture comprising the compound being alkylated and the ester alkylation agent, but lower proportions are feasible when using halosulfonic acids or aluminum chloride and the like as alkylation catalyst. The use of' superatmospheric pressures is generally advantageous, but normal or reduced pressures may also be used The reaction time should be adjusted with relation to the reactivities of the ester or esters and catalyst involved so .as to insure the desired amount of conversion. ,In the presence of conto insure adequate reaction of less reactive esters.

It is-preferred to use highly reactive alkylation catalysts, such as aluminum chloride and aluminum bromide and the'like, for alkylation of paraflins with estersof primary alcohols, par ticularly methyl and ethyl esters. In alkylating with esters of secondary and tertiary alcohols ester.

which are more subject to undesirable side reactions, it is preferabl to use milder alkylation catalysts such as sulfuric acid and aluminum chloride complexes, etc. r

T An excess of the ope or closed chain paraiiin being alkylated is desi able throughout the reaction. Smaller excesses may be used where less reactive organicacid esters are employed as the allwlating agent but with the more reactive tertiary and secondary esters of strong organic acids it is preferred to carry out the reaction with at least 1.5, more preferably at least 2, mols of the paramn being alkylated per mol of alkylation agent and most preferably with higher ratios of the order of to 100 to 1 or higher. Such high ratios may conveniently be achieved while employing more economical feed ratios of about 2.5 to 10 mols of isoparaflin per mol of ester by feeding the preferably premixed reactants into a stream of reaction mixture circulating in a closed circuit from which a part of the mixture is continuously withdrawn to a separator in which the bulk of the alkylation catalyst acid is withdrawn and returned to the circuit as described and claimed in United States Patent 2,232,674. Other which may be applied. For example, while alkylation of paraffins with esters of organic acids having' a dissociation constant greater than 2x10 has been emphasized, it is possible and sometimes very advantageous to carry out the alkylation produced by reaction of olefines with strong caroperation may be used.

In alkylating isobutane with normal propyl using a molar ratio of isobutane to propyl formate of about 80 to 1 in the reaction mixture and about equal volumes'oi catalyst and reactants at 25 C. and an average contact timeof 40 minutes, isobutane alkylation products which are almost identical with those obtained by reaction with isopropyl formate under the same conditions are produced. In both cases saturated hydrocarbons boiling between about 50 C. and 145 C. are formed. From these an 85% yield of aviation gasoline fraction having an octane number of about 89 may be separated.

The normal and secondary butyl formates likewise give very similar isobutane alkylation products under the same conditions. The hydrocarbon products are substantially completely saturated and have a specific gravity of about 0.70. About 95% boil below 150 C. and have'an octane number of v92. The corresponding products obtained by-alkylation of isobutane with isobutyl and tertiary butyl formates are very similar but may have a slightly higher octane number.

In operations such as these the strong organic acid set free in the reaction, aswell as any unreacted ester, appears for the most part in the hydrocarbon phase of the reacted mixture. These components may be readily separated, as by fractionation, from the reactionproducts and may then .be used for the preparation of more Alternatively, the mixture of alkylation products and free organic acid obtained in the alkylation may be used as feed to the esterification unit, preferably after removal of unreacted isoparaflin or other volatile components. This procedure is particularly advantageous when using esters of organic'acids which boil at or near the'boiling point of the desiredalkylation products.

It will be apparent that the invention ofiers many advantages over prior methods of alkylat ing isoparafilns, naphthalenes, and the like and that it is capable of wide variations not only with respect to the open and closed chain parafflns which may be alkylated and the esters of strong organic acids which may be reacted therewith but also in regard to the method of operation formate in the presence of 97% sulfuric acid,

boxylic acids are being employed it may be desirable to esterify only the more reactive tertiary oleflne content of the oleflnic mixture and to use as feed to the alkylation unit the tertiary esters and the unreacted secondary oleflne. Such a procedure offers the advantage of providing longer alkylation catalyst life than if the tertiary oleflnes are used as alkylatingagents along with the secondary oleflnes yet involves no less in yield of alkylate from removal of thetertiary olefines. Similar advantages may be obtained when the alkylation is carried out using the secondary oleflnes and tertiary esters of strong or- -ganic acids indiifrent alkylation Furthermore, although alkylation with the entire es- -ter content of an alkyl ester mixture has been from those of strong organic acid as well as for the removal of more reactive from less reactive esters of the same strong organic acid. Still other variations of the process may be carried out and it will therefore be understood that the invention is not limited to the details disclosed by way of illustration and example, nor by any theory suggested in explanation of. the improved results obtained.

I claim as my invention:

1. A process of alkylating isobutane which comprises reacting isobutane with isopropyl formate in' the presence of about 0.5 to 2 volumes of sulfiu-ie acid of atleast concentration per volume of said reactants at a temperature be-.

tween 0 C. and 40 C. r

2. A process of alkylating an isoparaflln which comprises reacting said isoparaflin with an ester of formic acid and an aliphatic secondary alco hol in the presence of concentrated sulfuric acid. 3. A process of alkylating an isoparaiiln which comprises reacting said isoparaflin with an ester of a carboxylic acid having a dissociation constant greater than 2 10 and an aliphatic tertiary alcohol in the 'presence iifconcentrated sulfuric acid.

4. A'process of alkylating an isoparaflln which comprises reacting said isoparaflin with an ester of an organic acid having a dissociation constant hydrocarbon having a tertiary carbon atom which comprises reacting said hydrocarbonwith an ester of an aliphatic monobasic carbozylic acid having a dissociation constant greater than 2x10- and an olefine in the presence 01 an inorganic acid alkylation catalyst.

' 7., A process of alkylating a saturated aliphatic hydrocarbon which comprises reacting said hydrocarbon with an ester of an organic acid havmg a dissociation constant greater than 2x 10* in the presence'of an alkylation catalyst.

8. A process oi alky'latinz isobutane whichcomprises reacting isobutane with a. mixture of a formic acid ester derived from a. tertiary olefin and the corresponding secondary olefin in the 

